Back to EveryPatent.com
United States Patent |
6,156,481
|
Takeda
,   et al.
|
December 5, 2000
|
Positive resist composition
Abstract
A hydroxystyrene-(meth)acrylate copolymer in which some phenolic hydroxyl
groups are crosslinked with acid labile groups is blended as a base resin
in a positive resist composition, which has the advantages of enhanced
dissolution inhibition and an increased dissolution contrast after
exposure.
Inventors:
|
Takeda; Takanobu (Nakakubiki-gun, JP);
Watanabe; Osamu (Nakakubiki-gun, JP);
Watanabe; Jun (Nakakubiki-gun, JP);
Hatakeyama; Jun (Nakakubiki-gun, JP);
Ohsawa; Youichi (Nakakubiki-gun, JP);
Ishihara; Toshinobu (Nakakubiki-gun, JP)
|
Assignee:
|
Shin-Etsu Chemical Co., Ltd. (Tokyo, JP)
|
Appl. No.:
|
428911 |
Filed:
|
October 28, 1999 |
Foreign Application Priority Data
| Oct 29, 1998[JP] | 10-307727 |
Current U.S. Class: |
430/270.1; 430/910 |
Intern'l Class: |
G03F 007/004 |
Field of Search: |
430/270.1,910
|
References Cited
U.S. Patent Documents
4491628 | Jan., 1985 | Ito et al. | 430/176.
|
4603101 | Jul., 1986 | Crivello | 430/270.
|
5252435 | Oct., 1993 | Tani et al. | 430/325.
|
5324804 | Jun., 1994 | Steinmann | 526/313.
|
5942367 | Aug., 1999 | Watanabe et al. | 430/170.
|
6033828 | Mar., 2000 | Shimada et al. | 430/270.
|
Foreign Patent Documents |
249139 | Dec., 1987 | EP.
| |
62-115440 | May., 1987 | JP.
| |
63-27829 | Feb., 1988 | JP.
| |
2-27660 | Jun., 1990 | JP.
| |
3-223858 | Oct., 1991 | JP.
| |
4-211258 | Aug., 1992 | JP.
| |
6-100488 | Apr., 1994 | JP.
| |
8-101509 | Apr., 1996 | JP.
| |
8-146610 | Jun., 1996 | JP.
| |
Other References
English abstract of JP 4211258, Aug. 1992.
English abstract of JP 8101509, Apr. 1996.
English abstract of JP 8146610, Jun. 1996.
|
Primary Examiner: Baxter; Janet
Assistant Examiner: Ashton; Rosemary
Attorney, Agent or Firm: Millen, White, Zelano & Branigan, P.C.
Claims
What is claimed is:
1. A positive resist composition comprising a polymer comprising recurring
units of the following general formula (1) and having a weight average
molecular weight of 1,000 to 500,000,
##STR8##
wherein R.sup.1 is hydrogen or methyl, R.sup.2 is an acid labile group,
R.sup.3, R.sup.4, R.sup.6, and R.sup.7 are independently hydrogen or
straight or branched alkyl groups of 1 to 6 carbon atoms, R.sup.5 is a
straight, branched or cyclic alkylene, alkylene ether, cyclohexylene or
arylene group of 1 to 10 carbon atoms, R.sup.8 is hydrogen, methyl, phenyl
or cyano group, R.sup.9 is hydrogen or a substituted or unsubstituted,
straight, branched or cyclic alkyl group of 1 to 10 carbon atoms wherein
the substituent is vinyl, acetyl, phenyl or cyano, p, r and s are positive
numbers and q is 0 or a positive number, satisfying
0<p/(p+q+r+s).ltoreq.0.8,0.ltoreq.q/(p+q+r+s).ltoreq.0.8, and
0<s/(p+q+r+s).ltoreq.0.9, zl is an integer of 1 to 3, z2 is an integer of
0 to 3, and the units may be of one or more types.
2. The positive resist composition of claim 1 wherein R.sup.9 is a tertiary
alkyl group of the following general formula (3):
##STR9##
wherein R.sup.10 is a methyl, ethyl, isopropyl, vinyl, acetyl, phenyl or
cyano group, and n is an integer of 0 to 3.
3. The positive resist composition of claim 1 wherein R.sup.9 is a tertiary
alkyl group of the following general formula (4):
##STR10##
wherein R.sup.11 is a vinyl, acetyl, phenyl or cyano group.
4. A chemical amplification type positive resist composition comprising:
(A) an organic solvent,
(B) a base resin in the form of a polymer according to claim 1, and
(C) a photoacid generator.
5. The resist composition of claim further comprising:
(E) a basic compound.
6. A chemical amplification type positive resist composition comprising:
(A) an organic solvent,
(B) a base resin in the form of a polymer according to claim 1,
(C) a photoacid generator, and
(D) a dissolution inhibitor.
7. The resist composition of claim 6 further comprising
(E) a basic compound.
8. A positive resist composition comprising a polymer comprising recurring
units of the following general formula (2) and having a weight average
molecular weight of 1,000 to 500,000,
##STR11##
wherein R.sup.1 is hydrogen or methyl, R.sup.8 is hydrogen, methyl, phenyl
or cyano group, R.sup.9 is hydrogen or a substituted or unsubstituted,
straight, branched or cyclic alkyl group of 1 to 10 carbon atoms wherein
the substituent is vinyl, acetyl, phenyl or cyano, p, r and s are positive
numbers and q is 0 or a positive number, satisfying
0<p/(p+q+r+s).ltoreq.0.8,0.ltoreq.q/(p+q+r+s).ltoreq.0.8, and
0<s/(p+q+r+s).ltoreq.0.9, z2 is an integer of 0 to 3, and the units may be
of one or more types.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention generally relates to a copolymer of hydroxystyrene and a
(meth)acrylate wherein some phenolic hydroxyl groups are crosslinked with
acid labile groups, and more particularly, to a positive working resist
composition, especially of the chemical amplification type, comprising the
copolymer as a base resin which has a much improved alkali dissolution
contrast before and after exposure, high sensitivity, and high resolution,
and is well suited as a micropatterning material for VLSI fabrication.
2. Prior Art
While a number of recent efforts are being made to achieve a finer pattern
rule in the drive for higher integration and operating speeds in LSI
devices, deep-ultraviolet lithography is thought to hold particular
promise as the next generation in microfabrication technology. Deep-UV
lithography is capable of achieving a minimum feature size of 0.5 .mu.m or
less and, when a resist having low light absorption is used, can form
patterns with sidewalls that are nearly perpendicular to the substrate.
Recently developed acid-catalyzed chemically amplified positive resists,
such as those described in JP-B 2-27660, JP-A 63-27829, U.S. PAT. NO.
4,491,628 and U.S. PAT. NO. 5,310,619, utilize a high-intensity KrF
excimer laser as the deep-UV light source. These resists, with their
excellent properties such as high sensitivity, high resolution, and good
dry etching resistance, are especially promising for deep-UV lithography.
Such chemically amplified positive resists include two-component systems
comprising a base resin and a photoacid generator, and three-component
systems comprising a base resin, a photoacid generator, and a dissolution
inhibitor having acid labile groups.
For example, JP-A 62-115440 describes a resist comprising
poly-p-tert-butoxystyrene and a photoacid generator. JP-A 3-223858
describes a similar two-component resist comprising a resin bearing
tert-butoxy groups within the molecule, in combination with a photoacid
generator. JP-A 4-211258 describes a two-component resist which is
comprised of polyhydroxystyrene bearing methyl, isopropyl, tert-butyl,
tetrahydropyranyl, or trimethylsilyl groups, together with a photoacid
generator. JP-A 6-100488 discloses a resist comprised of a
polydihydroxystyrene derivative, such as
poly[3,4-bis(2-tetrahydropyranyloxy)styrene],
poly[3,4-bis(tert-butoxy-carbonyloxy)styrene] or
poly[3,5-bis(2-tetrahydro-pyranyloxy)styrene], and a photoacid generator.
However, when the base resin in these resists bears acid labile groups on
side chains and these acid labile groups are groups such as tert-butyl and
tert-butoxycarbonyl which are cleaved by strong acids, the resist pattern
tends to take on a T-top profile. By contrast, since alkoxyalkyl groups
such as ethoxyethyl are cleaved by weak acids, their use has the drawback
that the pattern configuration considerably narrows as the time interval
between exposure and heat treatment increases. Moreover, the presence of
bulky groups on the side chains lowers the heat resistance of the resin
and makes it impossible to achieve a satisfactory sensitivity and
resolution. These problems have hitherto prevented the practical
implementation of either approach, and workable solutions have been
sought.
Other known resist compositions use (meth)acrylate copolymers for achieving
a higher transparency, improving the adhesion to the substrate and
restraining the footing to the substrate as disclosed in JP-A 8-101509 and
8-146610. The resist compositions of this type suffer from low heat
resistance and partial pattern collapse.
SUMMARY OF THE INVENTION
An object of the invention is to provide a positive working resist
composition, especially of the chemical amplification type, which has a
higher sensitivity, resolution, and exposure latitude than conventional
positive resist compositions and lends itself to the micropatterning
process.
The inventor has found that a polymer comprising recurring units of the
following general formula (1) or (2) and having a weight average molecular
weight of 1,000 to 500,000 is effective as a base resin in a positive
resist composition, especially a chemical amplification type positive
resist composition; that a chemical amplification type positive resist
composition comprising the polymer, a photoacid generator and an organic
solvent is improved in that the dissolution contrast of a resist film is
increased, especially the dissolution rate thereof after exposure is
increased, and has a high resolution, a high exposure latitude, and
improved process flexibility. The composition is thus well suited for
practical use and advantageously used in precise microfabrication,
especially in VLSI manufacture.
##STR1##
In the formulae, R.sup.1 is hydrogen or methyl, R.sup.2 is an acid labile
group, R.sup.3, R.sup.4, R.sup.6, and R.sup.7 are independently hydrogen
or straight or branched alkyl groups of 1 to 6 carbon atoms, R.sup.5 is a
straight, branched or cyclic alkylene, alkylene ether, cyclohexylene or
arylene group of 1 to 10 carbon atoms, R.sup.8 is hydrogen, methyl, phenyl
or cyano group, R.sup.9 is hydrogen or a substituted or unsubstituted,
straight, branched or cyclic alkyl group of 1 to 10 carbon atoms wherein
the substituent is vinyl, acetyl, phenyl or cyano. The units may be either
of one type or two or more different types. The letters p, r and s are
positive numbers and q is 0 or a positive number, satisfying
0<p/(p+q+r+s).ltoreq.0.8,0.ltoreq.q/(p+q+r+s).ltoreq.0.8, and
0<s/(p+q+r+s).ltoreq.0.9, z1 is an integer of 1 to 3, and z2 is an integer
of 0 to 3.
In the polymer of formula (1) or (2), some phenolic hydroxyl groups are
crosslinked with acid labile groups. When such a polymer is blended as a
base resin in a resist composition, the crosslinking with acid labile
groups offers to the composition the advantages of enhanced dissolution
inhibition and an increased dissolution contrast after exposure.
More particularly, a polymer having alkoxyalkyl groups added on side chains
alone is unlikely to take on a T-top profile because elimination reaction
takes place with weak acid, but has the drawback that because of its acid
sensitivity, the pattern configuration considerably narrows as the time
interval between exposure and heat treatment increases. Also, since the
polymer is less effective in inhibiting dissolution in base solutions, a
highly substituted polymer must be used to achieve a dissolution contrast,
but at the expense of heat resistance.
On the other hand, if a polymer in which phenolic hydroxyl groups on side
chains are protected with tert-butoxycarbonyl (t-BOC) groups is included
in the resist composition, the alkali dissolution inhibiting effects
improve, as a result of which dissolution contrast is achieved at a low
substitution ratio and the heat resistance is good. However, deprotection
to render the polymer alkali soluble requires a photoacid generator which
generates a strong acid such as trifluoromethanesulfonic acid.
Unfortunately, the use of such a strong acid tends to result in a T-top
profile as mentioned earlier.
Further, if a copolymer whose (meth)acrylic acid is protected with acid
labile groups is blended in the resist composition, there result the
drawbacks of partial pattern collapse and footing.
By contrast, the chemically amplified positive resist composition having
the polymer of formula (1) or (2) formulated as the base resin minimizes
the problems including the likelihood of T-top profiling, thinning of the
pattern configuration, low heat resistance, partial pattern collapse, and
footing. As a consequence, the chemically amplified positive resist
composition has a high sensitivity and resolution, is easy to control the
size and configuration of a resist pattern, and lends itself to the
micropatterning process.
Accordingly, in a first aspect, the invention provides a positive resist
composition comprising a polymer comprising recurring units of the general
formula (1) and having a weight average molecular weight of 1,000 to
500,000.
In a second aspect, the invention provides a positive resist composition
comprising an acrylate copolymer comprising recurring units of the general
formula (2) which is acetal crosslinked through a butylene group, and
especially protected with acid-eliminatable substituents represented by
the general formula (3) or (4) to be described later, and having a weight
average molecular weight of 1,000 to 500,000.
In a third aspect, the invention provides a chemical amplification type
positive resist composition comprising (A) an organic solvent, (B) the
above-defined polymer as a base resin, and (C) a photoacid generator.
In a fourth aspect, the invention provides a chemical amplification type
positive resist composition comprising (A) an organic solvent, (B) the
above-defined polymer as a base resin, (C) a photoacid generator, and (D)
a dissolution inhibitor.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Polymer
The high molecular weight compound of the invention is a copolymer
comprising units of the following general formula (1) or (2).
##STR2##
In formula (1) or (2), R.sup.1 is hydrogen or methyl, R.sup.2 is an acid
labile group, R.sup.3, R.sup.4, R.sup.6, and R.sup.7 are independently
hydrogen or straight or branched alkyl groups of 1 to 6 carbon atoms,
R.sup.5 is a straight, branched or cyclic alkylene, alkylene ether,
cyclohexylene or arylene group of 1 to 10 carbon atoms, R.sup.8 is
hydrogen, methyl, phenyl or cyano group, R.sup.9 is hydrogen or a
substituted or unsubstituted, straight, branched or cyclic alkyl group of
1 to 10 carbon atoms wherein the substituent is vinyl, acetyl, phenyl or
cyano. The units may be either of one type or two or more different types.
The letters p, r and s are positive numbers and q is 0 or a positive
number, satisfying
0<p/(P+q+r+s).ltoreq.0.8,0.ltoreq.q/(P+q+r+s).ltoreq.0.8, and
0<s/(P+q+r+s).ltoreq.0.9, zl is an integer of 1 to 3, and z2 is an integer
of 0 to 3.
The formulae (1) and (2) are described in more detail. R.sup.1 is hydrogen
or methyl. R.sup.2 is an acid labile group, which is selected from many
such groups, preferably tetrahydropyranyl, tetrafuranyl, and trialkylsilyl
groups in which the alkyl moieties each have 1 to 4 carbon atoms.
Exemplary alkyl groups represented by R.sup.3, R.sup.4, R.sup.6, and
R.sup.7 are methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, hexyl
and cyclohexyl.
Examples of the groups represented by R.sup.5 include alkylene groups such
as methylene, ethylene, propylene, butylene, hexylene, and octylene,
alkylene ether groups which are equal to the foregoing alkylene groups
having an intervening oxygen atom, cyclohexylene, phenylene and xylylene.
Those groups of 2 to 6 carbon atoms are preferable, and the straight
alkylene group having 4 carbon atoms, that is, butylene is most
preferable.
The unsubstituted alkyl groups represented by R.sup.9 are the same as the
above-exemplified alkyl groups. Preferably R.sup.9 is a tertiary alkyl
group serving as an acid labile group. More preferably, R.sup.9 is a
cyclic alkyl group of the following general formula (3):
##STR3##
wherein R.sup.10 is a methyl, ethyl, isopropyl, vinyl, acetyl, phenyl or
cyano group, and n is an integer of 0 to 3.
The cyclic alkyl groups of formula (3) are preferably 5-membered rings.
Examples include 1-methylcyclopentyl, 1-ethylcyclopentyl,
1-isopropylcyclopentyl, 1-vinylcyclopentyl, 1-acetylcyclopentyl,
1-phenylcyclopentyl, 1-cyanocyclopentyl, 1-methylcyclohexyl,
1-ethylcyclohexyl, 1-isopropylcyclohexyl, 1-vinylcyclohexyl,
1-acetylcyclohexyl, 1-phenylcyclohexyl, and 1-cyanocyclohexyl.
Also preferably, R.sup.9 is a substituted alkyl group of the following
general formula (4):
##STR4##
wherein R.sup.11 is a vinyl, acetyl, phenyl or cyano group. Exemplary such
alkyl groups include 1-vinyldimethyl, 1-acetyldimethyl, 1-phenyldimethyl
and 1 -cyanodimethyl.
When characteristics of a resist composition having the above-defined
polymer formulated as a base resin are taken into account, the letters p,
r and s are positive numbers and q is 0 or a positive number, satisfying
0<p/(p+q+r+s).ltoreq.0.8, preferably 0.02.ltoreq.p/(p+q+r+s), more
preferably p/(p+q+r+s).ltoreq.0.4;
0.ltoreq.q/(p+q+r+s).ltoreq.0.8, preferably
0.ltoreq.q/(p+q+r+s).ltoreq.0.5;
0<s/(p+q+r+s).ltoreq.0.9, preferably 0<s/(p+q+r+s).ltoreq.0.5, more
preferably 0<s/(p+q+r+s).ltoreq.0.3; and
0<r/(p+q+r+s).ltoreq.0.8, preferably 0<r/(p+q+r+s).ltoreq.0.7.
Further preferably, the letters satisfy
0<(p+q)/(p+q+r+s).ltoreq.0.8, more preferably
0.07.ltoreq.(p+q)/(p+q+r+s).ltoreq.0.5.
If any one of p, r and s is equal to 0 so that the polymer of formula (1)
does not contain the units associated therewith, the contrast of alkali
dissolution rate becomes low and the resolution becomes exacerbated. If
the ratio of p to the entirety (=p+q+r+s) is less than 0.02, there is a
likelihood of failing to take advantage of acid labile crosslinking
groups. If the ratio of p to the entirety exceeds 0.8, or if the ratio of
p+q to the entirety exceeds 0.8, the polymer would become gel and lose
alkali dissolution due to over-crosslinking, induce film thickness changes
and generation of internal stresses or bubbles upon alkali development,
and lose adhesion to the substrate due to reduced hydrophilic groups. If
the ratio of r to the entirety exceeds 0.8, the contrast of dissolution
rate would be exacerbated. If the ratio of s to the entirety is too high,
the alkali dissolution rate of unexposed areas becomes too low and the dry
etching resistance is lost. By properly selecting p, q, r and s within the
above ranges, it becomes possible to control the size and configuration of
a resist pattern.
In formula (1) or (2), zl is an integer of 1 to 3, and z2 is an integer of
0 to 3.
The content of the acid labile groups in the polymer has substantial
influence on the dissolution rate contrast of a resist film and governs
the properties of a resist composition relating to the size and
configuration of a resist pattern.
The polymer of the invention should have a weight average molecular weight
of 1,000 to 500,000, preferably 3,000 to 30,000. With a weight average
molecular weight of less than 1,000, resists would be less resistant to
heat. Too high a weight average molecular weight has a tendency that
alkali dissolution lowers and a footing phenomenon arises after pattern
formation.
It is understood that prior to crosslinking, a
hydroxystyrene-(meth)acrylate copolymer having a wide molecular weight
dispersity (Mw/Mn) contains more polymers of low molecular weight and high
molecular weight. Such a wide dispersity obstructs the design of the
number of crosslinks and it is rather difficult to reproduce resist
materials having the same properties. The influence of a molecular weight
and its dispersity becomes greater as the pattern rule becomes finer. In
order that a resist material be advantageously used in patterning features
to a finer size, the hydroxystyrene-(meth)acrylate copolymer should
preferably be a monodisperse one having a molecular weight dispersity of
1.0 to 2.0, especially 1.0 to 1.5.
The polymer of the invention is prepared by introducing acid labile
crosslinking groups into a hydroxystyrene-(meth)acrylate copolymer through
chemical reaction. This crosslinking reaction is effected by adding some
of the hydrogen atoms of hydroxyl groups in hydroxystyrene units to vinyl
groups in a divinyl ether compound (to be described just below) in the
presence of an acid catalyst, for thereby crosslinking and protecting some
of hydroxyl groups in polyhydroxystyrene (in a proportion of p mol per mol
of the overall hydroxyl groups) with alkoxyalkyl groups, as shown by the
following formula (5).
##STR5##
Herein, R.sup.1, R.sup.3 to R.sup.9, p, q, r and s are as defined above.
Exemplary divinyl ether compounds are divinyl ether derivatives including
ethylene glycol divinyl ether, diethylene glycol divinyl ether,
triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, neopentyl
glycol divinyl ether, hexanediol divinyl ether, tetraethylene glycol
divinyl ether, 1,4-di(vinyl ether methyl)cyclohexane, 1,4-di(vinyl ether
methoxy)benzene, and 1,4-di(vinyl ether ethoxy)benzene. It is preferred
that the crosslinking alkyl chain have 2 to 6 carbon atoms, and it is
especially preferred to use a divinyl ether compound having 4 carbon
atoms, that is, 1,4-butanediol divinyl ether.
The above reaction is preferably carried out in a solvent such as
dimethylformamide, tetrahydrofuran or dimethylacetamide. The acids used as
the catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic
acid, methanesulfonic acid, and p-toluenesulfonic acid pyridinium salt. An
appropriate amount of the acid used is 0.1 to 10 mol% based on the moles
of the overall hydroxyl groups in the polyhydroxystyrene to be reacted.
The reaction temperature is from room temperature to about 60.degree. C.
and the time is from about 1 to about 20 hours.
An alternative procedure of crosslinking and protecting some of the
hydroxyl groups in the polyhydroxystyrene with alkoxyalkyl groups is by
reacting an alkali hydride (e.g., NaH) or a base (e.g., triethylamine or
pyridine) and a haloethyl ether (e.g., 1,4-butanediol dichloroethyl ether)
with polyhydroxystyrene in the presence of a solvent (e.g., dimethyl
sulfoxide or tetrahydrofuran). In this procedure, the alkali hydride or
base is used in such amounts that a predetermined amount of crosslinking
groups is introduced per mol of the entire hydroxyl groups in the
polyhydroxystyrene. The reaction temperature is from 0.degree. C. to about
50.degree. C. and the time is from about 1 to about 20 hours.
Resist Composition
The chemical amplification type positive resist composition of the
invention contains (A) an organic solvent, (B) the above-defined polymer
as a base resin, (C) a photoacid generator, and optionally (D) a
dissolution inhibitor and (E) a basic compound.
The organic solvent used as component (A) in the invention may be any
organic solvent in which the photoacid generator, base resin, dissolution
regulator, and other components are soluble. Illustrative, non-limiting,
examples of the organic solvent include ketones such as cyclohexanone and
methyl-2-n-amylketone; alcohols such as 3-methoxybutanol,
3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol;
ethers such as propylene glycol monomethyl ether, ethylene glycol
monomethyl ether, propylene glycol monoethyl ether, ethylene glycol
monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol
dimethyl ether; and esters such as propylene glycol monomethyl ether
acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl
pyruvate, butyl acetate, methyl 3-methoxypropionate, and ethyl
3-ethoxypropionate. These solvents may be used alone or in combinations of
two or more thereof. Of the above organic solvents, diethylene glycol
dimethyl ether and 1-ethoxy-2-propanol are preferred because the photoacid
generator is most soluble therein.
The amount of the organic solvent used is preferably about 200 to 1,000
parts, more preferably about 400 to 800 parts by weight per 100 parts by
weight of the base resin (B).
The photoacid generators (C) used in the resist composition of the
invention include onium salts of the general formula (6) below,
diazomethane derivatives of formula (7), glyoxime derivatives of formula
(8), .beta.-ketosulfone derivatives, disulfone derivatives,
nitrobenzylsulfonate derivatives, sulfonic acid ester derivatives, and
imidoyl sulfonate derivatives.
(R.sup.30).sub.b M.sup.+ K.sup.- (6)
In the formula, R.sup.30 is a normal, branched or cyclic alkyl group of 1
to 12 carbon atoms, an aryl group of 6 to 12 carbon atoms, or an aralkyl
group of 7 to 12 carbon atoms; M.sup.+ is iodonium or sulfonium; K.sup.-
is a non-nucleophilic counter-ion; and the letter b is equal to 2 or 3.
Illustrative examples of alkyl groups represented by R.sup.30 include
methyl, ethyl, propyl, butyl, cyclohexyl, 2-oxocyclohexyl, norbornyl, and
adamantyl. Exemplary aryl groups include phenyl; alkoxyphenyl groups such
as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxy-phenyl,
p-tert-butoxyphenyl, and m-tert-butoxyphenyl; and alkylphenyl groups such
as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl,
4-tert-butylphenyl, 4-butylphenyl and dimethylphenyl. Exemplary aralkyl
groups include benzyl and phenethyl. Examples of the non-nucleophilic
counter-ion represented by K.sup.- include halide ions such as chloride
and bromide ions; fluoroalkylsulfonate ions such as triflate,
1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate;
arylsulfonate ions such as tosylate, benzenesulfonate,
4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; and
alkylsulfonate ions such as mesylate and butanesulfonate.
##STR6##
In the formula, R.sup.31 and R.sup.32 are normal, branched or cyclic alkyl
or halogenated alkyl groups of 1 to 12 carbon atoms, aryl or halogenated
aryl groups of 6 to 12 carbon atoms, or aralkyl groups of 7 to 12 carbon
atoms.
Illustrative examples of alkyl groups represented by R.sup.31 and R.sup.32
include methyl, ethyl, propyl, butyl, amyl, cyclopentyl, cyclohexyl,
norbornyl, and adamantyl. Exemplary halogenated alkyl groups include
trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, and
nonafluorobutyl. Exemplary aryl groups include phenyl; alkoxyphenyl groups
such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl,
p-tert-butoxyphenyl, and m-tert-butoxyphenyl; and alkylphenyl groups such
as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl,
4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl. Exemplary
halogenated aryl groups include fluorobenzene, chlorobenzene, and
1,2,3,4,5-pentafluorobenzene. Exemplary aralkyl groups include benzyl and
phenethyl.
##STR7##
In the formula, R.sup.33, R.sup.34 and R.sup.35 are normal, branched or
cyclic alkyl or halogenated alkyl groups of 1 to 12 carbon atoms, aryl or
halogenated aryl groups of 6 to 12 carbon atoms, or aralkyl groups of 7 to
12 carbon atoms. R.sup.34 and R.sup.35 may together form a cyclic
structure with the proviso that when they form a cyclic structure, each is
a normal or branched alkylene group of 1 to 6 carbon atoms.
The alkyl, halogenated alkyl, aryl, halogenated aryl, and aralkyl groups
represented by R.sup.33, R.sup.34 and R.sup.35 are exemplified by the same
groups mentioned above for R.sup.31 and R.sup.32. Examples of alkylene
groups represented by R.sup.34 and R.sup.35 include methylene, ethylene,
propylene, butylene, and hexylene.
Illustrative examples of the photoacid generator include:
onium salts such as diphenyliodonium trifluoromethane-sulfonate,
(p-tert-butoxyphenyl)phenyliodonium trifluoro-methanesulfonate,
diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl) phenyliodonium
p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate,
(p-tert-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate,
bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethane-sulfonate,
tris(p-tert-butoxyphenyl)sulfonium trifluoro-methanesulfonate,
triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)
diphenylsulfonium p-toluenesulfonate,
bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate,
tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium
nonafluorobutanesulfonate, triphenyl-sulfonium butanesulfonate,
trimethylsulfonium trifluoro-methanesulfonate, trimethylsulfonium
p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium
trifluoromethane-sulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium
p-toluenesulfonate, dimethylphenylsulfonium trifluoro-methanesulfonate
methanesulfonate, dimethylphenylsulfonium p-toluenesulfonate,
dicyclohexylphenylsulfonium trifluoromethanesulfonate, and
dicyclohexylphenylsulfonium p-toluenesulfonate;
diazomethane derivatives such as bis(benzenesulfonyl)-diazomethane,
bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane,
bis(cyclohexylsulfonyl)-diazomethane,
bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl) diazomethane,
bis(isobutylsulfonyl)-diazomethane, bis(sec-butylsulfonyl)diazomethane,
bis(n-propylsulfonyl) diazomethane, bis(isopropylsulfonyl)-diazomethane,
diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(n-amylsulfonyl)
diazomethane, bis(isoamylsulfonyl)diazomethane,
bis(sec-amylsulfonyl)diazomethane, bis(tert-amylsulfonyl)-diazomethane,
1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)-diazomethane, diazomethane,
1-cyclohexylsulfonyl-1-(tert-amylsulfonyl)-diazomethane, and
1-tert-amylsulfonyl-1-(tert-butyl-sulfonyl) diazomethane;
glyoxime derivatives such as
bis-o-(p-toluene-sulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(p-toluenesulfonyl)-.alpha.-diphenylglyoxime,
bis-o-(p-toluenesulfonyl)-.alpha.-dicyclohexyl-glyoxime,
bis-o-(p-toluenesulfonyl)-2,3-pentanedioneglyoxime,
bis-o-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime,
bis-o-(n-butanesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(n-butanesulfonyl) -.alpha.-diphenylglyoxime,
bis-o-(n-butanesulfonyl) -.alpha.-dicyclohexylglyoxime, bis-o-(n-25
butanesulfonyl)-2,3-pentanedioneglyoxime,
bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedioneglyoxime,
bis-o-(methanesulfonyl) -.alpha.-dimethylglyoxime,
bis-o-(trlifluoro-methanesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(1,1,1-trifluoroethanesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(tert-butanesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(perfluorooctane-sulfonyl)-.alpha.dimethylglyoxime,
bis-o-(cyclohexanesulfonyl)-.alpha.-dimethylglyoxime,
bis-o-(benzenesulfonyl)-.alpha.-dimethyl-glyoxime,
bis-o-(p-fluorobenzenesulfonyl)-.alpha.-dimethyl-glyoxime,
bis-o-(p-tert-butylbenzenesulfonyl)-.alpha.-dimethyl-glyoxime,
bis-o-(xylenesulfonyl)-.alpha.-dimethylglyoxime, and
bis-o-(camphorsulfonyl)-.alpha.-dimethylglyoxime;
.beta.-ketosulfone derivatives such as
2-cyclohexyl-carbonyl-2-(p-toluenesulfonyl)propane and
2-isopropyl-carbonyl-2-(p-toluenesulfonyl)propane;
disulfone derivatives such as diphenyl disulfone and dicyclohexyl
disulfone;
nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl
p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate;
sulfonic acid ester derivatives such as 1,2,3-tris(methanesulfonyloxy)
benzene, 1,2,3-tris(trifluoro-methanesulfonyloxy)benzene, and
1,2,3-tris(p-toluene-sulfonyloxy)benzene; and
imidoyl sulfonate derivatives such as phthalimidoyl triflate, phthalimldoyl
tosylate, 5-norbornene-2,3-dicarboxyimidoyl triflate,
5-norbornene-2,3-dicarboxyimidoyl tosylate, and
5-norbornene-2,3-dicarboxyimidoyl n-butylsulfonate.
Preferred among these photoacid generators are onium salts such as
triphenylsulfonium trifluoromethanesulfonate,
(p-tert-butoxyphenyl)diphenylsulfonium trifluoromethane-sulfonate,
tris(p-tert-butoxyphenyl)sulfonium trifluoro-methanesulfonate,
triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)
diphenylsulfonium p-toluenesulfonate, and
tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate; diazomethane
derivatives such as bis(benzenesulfonyl)-diazomethane,
bis(p-toluenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane,
bis(n-butylsulfonyl)-diazomethane, bis(isobutylsulfonyl)diazomethane,
bis(sec-butylsulfonyl) diazomethane, bis(n-propylsulfonyl)diazomethane,
bis(isopropylsulfonyl)diazomethane, and bis(tert-butylsulfonyl)
diazomethane; and glyoxime derivatives such as
bis-o-(p-toluenesulfonyl)-.alpha.-dimethylglyoxime and
bis-o-(n-butanesulfonyl)-.alpha.- dimethylglyoxime. These photoacid
generators may be used singly or in admixture of two or more. Onium salts
are effective for improving rectangularity, while diazomethane derivatives
and glyoxime derivatives are effective for reducing standing waves. The
combination of an onium salt with a diazomethane or a glyoxime derivative
allows for finer adjustment of the profile.
The photoacid generator is preferably added in an amount of 0.2 to 20
parts, and especially 0.5 to 15 parts by weight, per 100 parts by weight
of the entire base resin. Smaller amount of the photoacid generator would
generate a less amount of acid upon exposure, leading to low sensitivity
and resolution. Larger amount of the photoacid generator would lower the
transmittance of resist to detract from resolution.
To the resist composition, a dissolution inhibitor (D) may be added. The
preferred dissolution inhibitor is a compound having a weight average
molecular weight of 100 to 1,000 and having on the molecule at least two
phenolic hydroxyl groups, in which an average of from 10 to 100 mol% of
all the hydrogen atoms on the phenolic hydroxyl groups have been replaced
with acid labile groups. The compound has a weight average molecular
weight of 100 to 1,000, and preferably 150 to 800. The dissolution
inhibitors may be used alone or in admixture of two or more. The amount of
the dissolution inhibitor added is preferably 0 to about 50 parts, more
preferably about 5 to 50 parts, and most preferably about 10 to 30 parts
by weight per 100 parts by weight of the base resin. Less amounts of the
dissolution inhibitor may fail to yield an improved resolution, whereas
excessive amounts would lead to thinning of the patterned film, and thus a
decline in resolution.
In the resist composition, a basic compound (E) may be blended. The basic
compound used as component (E) is preferably a compound capable of
suppressing the rate of diffusion when the acid generated by the photoacid
generator diffuses within the resist film. The inclusion of this type of
basic compound holds down the rate of acid diffusion within the resist
film, resulting in better resolution. In addition, it suppresses changes
in sensitivity following exposure and reduces substrate and environment
dependence, as well as improving the exposure latitude and the pattern
profile. Examples of basic compounds include primary, secondary, and
tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic
amines, carboxyl group-bearing nitrogenous compounds, sulfonyl
group-bearing nitrogenous compounds, hydroxyl group-bearing nitrogenous
compounds, hydroxyphenyl group-bearing nitrogenous compounds, alcoholic
nitrogenous compounds, and amide derivatives.
Examples of suitable primary aliphatic amines include ammonia, methylamine,
ethylamine, n-propylamine, isopropyl-amine, n-butylamine, iso-butylamine,
sec-butylamine, tert-butylamine, pentylamine, tert-amylamine,
cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine,
nonylamine, decylamine, dodecylamine, cetylamine, methylene-diamine,
ethylenediamine, and tetraethylenepentamine. Examples of suitable
secondary aliphatic amines include dimethylamine, diethylamine,
di-n-propylamine, di-iso-propylamine, di-n-butylamine, di-iso-butylamine,
di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine,
dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine,
didecylamine, didodecylamine, dicetylamine, N,N-dimethylmethylenediamine,
N,N-dimethylethylenediamine, and N,N-dimethyltetraethylenepentamine.
Examples of suitable tertiary aliphatic amines include trimethylamine,
triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-n-butylamine,
tri-iso-butylamine, tri-sec-butylamine, tripentylamine,
tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine,
trioctylamine, trinonylamine, tridecylamine, tridodecylamine,
tricetylamine, N,N,N',N'-tetramethylmethylenediamine,
N,N,N',N'-tetramethylethylenediamine, and
N,N,N',N'-tetramethyl-tetraethylenepentamine.
Examples of suitable mixed amines include dimethyl-ethylamine,
methylethylpropylamine, benzylamine, phenethylamine, and
benzyldimethylamine. Examples of suitable aromatic and heterocyclic amines
include aniline derivatives (e.g., aniline, N-methylaniline,
N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline,
3-methylaniline, 4-methylaniline, ethylaniline, propylaniline,
trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline,
2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, and
N,N-dimethyltoluidine), diphenyl(p-tolyl)amine, methyldiphenylamine,
triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene,
pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole,
2,4-dimethylpyrrole, 2,5-dimethylpyrrole, and N-methylpyrrole), oxazole
derivatives (e.g., oxazole and isooxazole), thiazole derivatives (e.g.,
thiazole and isothiazole), imidazole derivatives (e.g., imidazole,
4-methylimidazole, and 4-methyl-2-phenylimidazole), pyrazole derivatives,
furazan derivatives, pyrroline derivatives (e.g., pyrroline and
2-methyl-1-pyrroline), pyrrolidine derivatives (e.g., pyrrolidine,
N-methylpyrrolidine, pyrrolidinone, and N-methylpyrrolidone), imidazoline
derivatives, imidazolidine derivatives, pyridine derivatives (e.g.,
pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine,
4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine,
triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine,
4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine,
butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone,
4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine,
2-(1-ethylpropyl)pyridine, aminopyridine, and dimethylaminopyridine),
pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives,
pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives,
piperazine derivatives, morpholine derivatives, indole derivatives,
isoindole derivatives, 1H-indazole derivatives, indoline derivatives,
quinoline derivatives (e.g., quinoline and 3-quinolinecarbonitrile),
isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives,
quinoxaline derivatives, phthalazine derivatives, purine derivatives,
pteridine derivatives, carbazole derivatives, phenanthridine derivatives,
acridine derivatives, phenazine derivatives, 1,10-phenanthroline
derivatives, adenine derivatives, adenosine derivatives, guanine
derivatives, guanosine derivatives, uracil derivatives, and uridine
derivatives.
Examples of suitable carboxyl group-bearing nitrogenous compounds include
aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (e.g.
nicotinic acid, alanine, alginine, aspartic acid, glutamic acid, glycine,
histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine,
threonine, lysine, 3-aminopyrazine-2-carboxylic acid, and methoxyalanine).
Examples of suitable sulfonyl group-bearing nitrogenous compounds include
3-pyridinesulfonic acid and pyridinium p-toluenesulfonate. Examples of
suitable hydroxyl group-bearing nitrogenous compounds, hydroxyphenyl
group-bearing nitrogenous compounds, and alcoholic nitrogenous compounds
include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol,
3-indolemethanol hydrate, monoethanolamine, diethanolamine,
triethanolamine, N-ethyldiethanolamine, N,N-diethyl- ethanolamine,
triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol,
3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl) morpholine,
2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl) piperazine,
1-[2-(2-hydroxyethoxy)ethyl]-peperazine, piperidine ethanol,
1-(2-hydroxyethyl)-pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone,
3-piperidino-1,2-propanediol, 1,2-propanediol,
3-pyrrolidino-1,2-propanediol, 8-hydroxyjulolidine, 3-quinuclidinol,
3-tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol,
N-(2-hydroxyethyl) phthalimide, and N-(2-hydroxyethyl)-isonicotinamide.
Examples of suitable amide derivatives include formamide,
N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide,
N,N-dimethylacetamide, propionamide, and benzamide. Suitable imide
derivatives include phthalimide, succinimide, and maleimide.
Compounds in which some or all of hydroxyl groups of the hydroxyl
group-bearing nitrogenous compounds are replaced by methyl group, ethyl
group, methoxymethyl group, methoxyethoxymethyl group, acetyl group or
ethoxyethyl group may also be used. Preferred are methyl substituents,
acetyl substituents, methoxymethyl substituents and methoxyethoxy-methyl
substituents of ethanolamine, diethanolamine, and triethanolamine.
Examples include tris(2-methoxyethyl)amine, tris(2-ethoxyethyl)amine,
tris(2-acetoxyethyl)amine, tris{2-(methoxyethoxy)ethyl}amine,
tris{2-(methoxyethoxy)-ethyl}amine,
tris[2-{(2-methoxyethoxy)methoxy}ethyl]amine,
tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine,
tris{2-(1-ethoxyethoxy)ethyl}-amine, tris{2-(1-ethoxypropoxy)ethyl}amine,
tris[2-{(2-hydroxyethoxy)ethoxy}ethyl]amine.
The basic compounds may be used singly or in combination of two or more.
The basic compound is preferably formulated in an amount of 0 to 2 parts
by weight, and especially 0.01 to 1 part by weight per 100 parts by weight
of the solid matter in the resist composition. The larger amount of the
basic compound would result in too low a sensitivity.
The resist composition of the invention may include, as optional
ingredients, a surfactant for improving the coating characteristics and a
light absorbing compound for minimizing the influence of diffuse
reflection from the substrate. Optional ingredients may be added in
conventional amounts so long as this does not compromise the objects of
the invention. Exemplary surfactants include perfluoroalkyl
polyoxyethylene ethanols, fluorinated alkyl esters, perfluoroalkylamine
oxides, and perfluoroalkyl EO adducts. Exemplary light absorbing compounds
are diarylsulfoxides, diarylsulfones, 9,10-dimethylanthracene, and
9-fluorenone.
Pattern formation using the positive resist composition of the invention
may be carried out by a known lithographic technique. For example, the
resist composition may be applied onto a substrate such as a silicon wafer
by spin coating to form a resist film having a thickness of 0.5 to 2.0
.mu.m, which is then pre-baked at 80 to 120.degree. C. The resist film is
exposed to high-energy radiation such as deep-UV radiation, electron beams
or x-rays, post-exposure baked (PEB) at 70 to 120.degree. C. for 30 to 200
seconds, and developed with a base solution. Of the various types of
high-energy radiation that may be used, the resist composition of the
invention is best suited to fine pattern formation with deep-UV rays
having a wavelength of 193 to 254 nm and electron beams.
The positive working resist composition of the invention is sensitive to
high-energy radiation, has excellent sensitivity, resolution, and plasma
etching resistance, and provides a resist pattern having outstanding heat
resistance. Moreover, the resulting pattern is less prone to overhang
formation and has an excellent dimensional controllability. The drawbacks
of partial pattern collapse and footing inherent to (meth)acrylic acid
copolymers are eliminated. Because these features of the inventive resist
composition enable its use particularly as a resist having a low
absorption at the exposure wavelength of a KrF excimer laser, a finely
defined pattern having sidewalls perpendicular to the substrate can easily
be formed, making the resist ideal as a micropatterning material in VLSI
fabrication.
EXAMPLE
Examples of the invention are given below by way of illustration and not by
way of limitation.
Synthetic Example 1
Into a 2-liter flask were admitted 93.8 g of .alpha.-methylhydroxystyrene,
54.7 g of 1-ethylcyclopentyl methacrylate, and 1.5 liters of THF as a
solvent. The reactor was cooled to -70.degree. C. in a nitrogen
atmosphere, and the step of evacuation and deaeration followed by nitrogen
flow was repeated three times. The reactor was warmed up to room
temperature, 13.1 g of AIBN was added as a polymerization initiator, and
the reactor was heated to 60.degree. C., whereupon reaction was effected
for 15 hours. The reaction solution was concentrated to a half volume and
poured into 10 liters of water whereupon white solids precipitated. By
filtration and vacuum drying at 60.degree. C., 120 g of a white polymer
was obtained. The resulting copolymer, designated Poly-1, was analyzed by
.sup.13 C-NMR, .sup.1 H-NMR, and GPC, with the results shown below.
Copolymer compositional ratio (molar ratio)
.alpha.-methylhydroxystyrene:1-ethylcyclopentyl methacrylate=69:31
Weight average molecular weight (Mw)=12,000
Dispersity (Mw/Mn)=1.48
Synthetic Example 2
A copolymer, designated Poly-2, was prepared by the same procedure as in
Synthetic Example 1 using .alpha.-methylhydroxystyrene and
1-phenyldimethyl methacrylate. The results of analysis are given below.
Copolymer compositional ratio (molar ratio)
.alpha.-methylhydroxystyrene:1-phenyldimethyl methacrylate=72:28
Weight average molecular weight (Mw)=14,000
Dispersity (Mw/Mn)=1.62
Synthetic Example 3
Into a 2-liter flask were admitted 113.4 g of hydroxystyrene, 54.7 g of
1-ethylcyclopentyl methacrylate, and 1.5 liters of THF as a solvent. The
reactor was cooled to -70.degree. C. in a nitrogen atmosphere, and the
step of evacuation and deaeration followed by nitrogen flow was repeated
three times. The reactor was warmed up to room temperature, 13.1 g of AIBN
was added as a polymerization initiator, and the reactor was heated to
60.degree. C., whereupon reaction was effected for 15 hours. The reaction
solution was concentrated to a half volume and poured into 10 liters of
water whereupon white solids precipitated. By filtration and vacuum drying
at 60.degree. C., 132 g of a white polymer was obtained. The polymer was
dissolved in 1.0 liter of ethanol again, to which 50 g of sodium hydroxide
was added to effect deprotection reaction. While being cooled, the
reaction solution was neutralized with 28wt % hydrochloric acid. The
reaction solution was concentrated and then dissolved in 0.5 liter of
acetone, followed by precipitation, filtration and drying as above. There
was obtained 109 g of a white copolymer. The copolymer, designated Poly-3,
was analyzed by .sup.13 C-NMR, .sup.1 H-NMR, and GPC, with the results
shown below.
Copolymer compositional ratio (molar ratio)
hydroxystyrene:1-ethylcyclopentyl methacrylate=72:28
Weight average molecular weight (Mw)=12,000
Dispersity (Mw/Mn)=1.49
Synthetic Example 4
A copolymer, designated Poly-4, was prepared by the same procedure as in
Synthetic Example 3 using hydroxystyrene and 1-phenyldimethyl
methacrylate. The results of analysis are given below.
Copolymer compositional ratio (molar ratio) hydroxystyrene:1-phenyldimethyl
methacrylate=75:25
Weight average molecular weight (Mw)=13,000
Dispersity (Mw/Mn)=1.41
Synthetic Example 5
In a 2-liter flask, 50 g of the .alpha.-methylhydroxy-
styrene/1-ethylcyclopentyl methacrylate copolymer (Poly-1) was dissolved
in 0.5 liter of THF in a nitrogen atmosphere. Triethylamine, 2.0 g, was
added, and with stirring at 0.degree. C., 1,4-butanediol dichloroethyl
ether was added dropwise. After one hour of reaction, the reaction
solution was poured into 5 liters of water containing 20 ml of acetic acid
for precipitation. The solids collected by filtration were dissolved in
acetone again. The solids were precipitated from 5 liters of water again,
filtered and vacuum dried. The polymer, designated Poly-5, was analyzed by
.sup.1 H-NMR to find that 4.5% of hydrogen atoms of hydroxyl groups in
polyhydroxystyrene was crosslinked.
Synthetic Example 6
By the same procedure as in Synthetic Example 5, crosslinking reaction was
carried out on the copolymers, Poly-2, Poly-3 and Poly-4. There were
obtained crosslinked polymers, Poly-6, Poly-7 and Poly-8 having the
following percent crosslink.
______________________________________
Designation Starting copolymer
% crosslink
______________________________________
Poly-6 Poly-2 4.1%
Poly-7 Poly-3 6.6%
Poly-8 Poly-4 5.2%
______________________________________
Examples and Comparative Examples
Resist compositions were formulated by dissolving 80 parts by weight of
each of the crosslinked polymers obtained in the foregoing Synthesis
Examples, Poly-5 to Poly-8 as the base resin, 3 parts by weight of
triphenylsulfonium p-toluenesulfonate as the photoacid generator, 0.1 part
by weight of triethanol amine as the basic compound, and 0.2 part by
weight of 2,2-bis(4-t-butylcarboxyphenyl)propane as the dissolution
inhibitor in 530 parts by weight of a 7/3 mixture of propylene glycol
monoethyl acetate and ethyl lactate. These compositions were each passed
through a 0.2-micron Teflon filter to give the finished resist solution.
For comparison purposes, resist solutions were similarly prepared using
each of the polymers, Poly-1 to Poly-4 as the base resin.
Each resist solution was spin coated onto a silicon wafer, following which
the coated silicon wafer was baked on a hot plate at 100.degree. C. for
120 seconds. The resist film had a thickness of 0.8 .mu.m. The resist film
was exposed using an excimer laser stepper (NSR-2005EX8A, from Nikon
Corporation; NA=0.5), then baked at 90.degree. C. for 60 seconds and
developed with a 2.38% solution of tetramethylammonium hydroxide in water,
thereby giving a positive pattern. The resist patterns obtained were
evaluated as described below.
First, the sensitivity (Eth) was determined. Next, the optimal exposure
dose (sensitivity: Eop) was defined as the dose which provides a 1:1
resolution at the top and bottom of a 0.35 .mu.m line-and-space pattern.
The resolution of the resist under evaluation was defined as the minimum
line width of the lines and spaces that separated at this dose. The shape
of the resolved resist pattern was examined under a scanning electron
microscope. Also, a 0.22 .mu.m line-and-space pattern was observed for
irregularities (partial pattern collapse and footing) under a scanning
electron microscope.
The results are shown in Table 1.
TABLE 1
______________________________________
Resolution Partial pattern
Polymer (.mu.m) collapse Footing
______________________________________
E1 Poly-5 0.18 slight Good
E2 Poly-6 0.18 none Good
E3 Poly-7 0.18 none Good
E4 Poly-8 0.18 slight Excellent
CE1 Poly-1 0.2 collapsed
Poor
CE2 Poly-2 0.2 slight Fair
CE3 Poly-3 0.18 collapsed
Poor
CE4 Poly-4 0.18 collapsed
Fair
______________________________________
As is evident from Table 1, the chemically amplified positive resist
compositions of the invention provide resist patterns having a high
resolution, minimized partial pattern collapse and minimized footing.
Japanese Patent Application No. 10-307727 is incorporated herein by
reference.
Although some preferred embodiments have been described, many modifications
and variations may be made thereto in light of the above teachings. It is
therefore to be understood that the invention may be practiced otherwise
than as specifically described without departing from the scope of the
appended claims.
Top